Thiamine z-ethylhexyl sulfate



Patented May 3, 1949 UNITED STATES PATENT OFFICE THIAlVIINE Z-ETHYLHEXYL SULFATE No Drawing.

Original application March 20,

1944, Serial No. 527,343. Divided and this application February 19, 1948, Serial No. 9,634

1 Claim.

This invention relates to sparingly Watersoluble salts of thiamine and to a process for preparing them.

It is a principal object of this invention to provide as fortifying agents physiologically active salts of thiamine suitable for use in those instances where a fortifying agent of low Watersolubility is desired, for instance, in the enrichment of cereals subjected to rinsing before being cooked.

In certain regions, especially in the southern States, cereals such as hominy and rice form an important part of the human diet. Since modern methods of preparing cereal crops for use as food result in the removal of the major portion of the vitamin content, the cereal becomes a poor source of thiamine. However, cereals are an excellent source of carbohydrates and it is desirable to increase their food value by adding to them certain nutritive substances, including thiamine.

A frequently-used method for food enrichment consists in spraying the food with a solution of the fortifying agent and subsequently evaporating the solvent to leave a coating of the fortifying agent on the food particles. In an alternative method the fortifying agent is added in solid form and thoroughly mixed with the food, the particle size of the fortifying agent being conditioned somewhat by that of the food, since an even distribution should be maintained.

Neither of the above methods is satisfactory for the addition of thiamine to the grains of cereals. It is customary among consumers of hoininy and rice, for example, to subject the particles before cooking to a more or less vigorous rinsing with water, any particles of abnormal appearance being picked out and discarded. Thiamine, being water-soluble, is quickly dissolved from the particles if it has been applied by means of a spray; or, if it has been added as a solid, it is either dissolved or is likely to be removed because of its physical appearance.

The thiamine salts prepared according to the present invention are especially adapted to the overcoming of the previous difficulties encountered in producing enriched cereals. These salts are at least as active physiologically as thiamine chloride hydrochloride and are capable of being fixed upon the surface of cereal particles in such a manner as to avoid loss of .vitamin B1 by rinsing.

The compounds of our invention are prepared by bringing together aqueous solutions of a watersoluble thiamine salt and an acid, or a watersoluble salt thereof, selected from the class consisting of Z-ethylhexyl hydrogen sulfate, cholestenone-G-sulfonic acid, and methane-1-,1-bis- (2-hydroxy-3-naphthoic acid). The precipitate which forms is readily purified by recrystallization, if necessary.

Our invention is illustrated by the following examples but is not limited thereto.

Example 1 A solution of 6.74 g. of thiamine chloride hydrochloride in 25 ml. of water is mixed with 18.6 g. of a 25% solution of sodium 2-ethylhexyl sulfate. Within an hour a precipitate begins to form and after cooling the solution in an ice bath for several hours the colorless crystals are collected on a filter. After two recrystallizatio-ns from 50 ml. portions of water at C. there is obtained 4.5 g. of thiamine Z-ethylhexyl sulfate, C28H52N4S309, M. P. approximately 148-149 C.

Example 2 A solution of 1.69 g. of thiamine chloride hydrochloride in 30 ml. of water and a solution of 2.17 g, of cholestenone-G-sulfonic acid in 30 ml. of water are run simultaneously with vigorous stirring during a period of thirty minutes into 50 ml. of water. Precipitation begins immediately and after stirring for another hour the white precipitate is filtered off. After three recrystallizations of this product from dilute alcohol, there is obtained 2.3 g. of thiamine cholestenone-B-sulfonate, Cs6H102N4S3O9. It decomposes slowly above 200 C.

Example 3 Six and seventy-four hundredths grams of thiamine chloride hydrochloride and 4.5 g. of sodium methane-1,1-bis-(2-hydroxy-3-naphthoate) are each dissolved in 100 ml. portions of water. The two solutions are run simultaneously with vigorous stirring during a period of thirty minutes into 200 ml. of water. A precipitate forms immediately, and after stirring the solution one hour longer, the pale yellow solid is separated, washed with water until free of chloride ion and dried. The product is purified by recrystallizing twice from aqueous peroxide-free dioxane. There is obtained as the dihydrate 4.3 g. of thiamine methane 1,1 bis (2 hydroxy 3 naphthoate) C35H32N4SO'L2H2O, M. P. above 350 C.

The present application is a division of our pending U. S. patent application Ser. No. 527,343, filed March 20, 1944, now Patent No. 2,460,009.

We claim:

The sparingly water-soluble salt thiamine 2-ethylhexyl sulfate, having the molecular formula C2sH52N4SaO'9 and being characterized by melting at approximately 148-149.

WOLFGANG HUBER. WERNER R. BOEHME.

N 0 references cited. 

